ACHIEVE. In this issue: Processing Tight Oils in FCC: Issues, Opportunities and Flexible Catalytic Solutions

Transcription

1 No. 114 / Spring 2014/ Catalagram A Catalysts Technologies Publication In this issue: p Processing Tight Oils in FCC: Issues, Opportunities and Flexible Catalytic Solutions p p p Tight Oil Distillate in ULSD Production, What To Expect? Two Companies Joined to Develop a Catalytic Solution for Bottoms Upgrading to Diesel in the FCC Unit Meeting Tier 3 Gasoline Sulfur Regulations ACHIEVE THE ADVANTAGE Grace FCC Catalyst

2 Grace FCC Catalysts and Additives Innovative Catalytic Solutions Industry s Broadest Catalyst Portfolio Flexible Functionality for Processing Unconventional Feeds Global Manufacturing Footprint World-class R&D Industry-leading Technical Service

3 3 Processing Tight Oils in FCC: Issues, Opportunities and Flexible Catalytic Solutions By Kenneth Bryden, Michael Federspiel, E. Thomas Habib, Jr. and Rosann Schiller, Grace Catalysts Technologies Tight oils (shale oils) are becoming a major feed source for North American refineries. Problems in treating these feedstocks are contaminant metals, heat balance effects, and the overall refinery configuration. This paper provides details on cracking these feedstocks and the application of new catalyst technologies and unit operating strategies to maximize product value. Tight Oil Distillate in ULSD Production, What To Expect? By Greg Rosinski, Brian Watkins and Charles Olsen, Advanced Refining Technologies This article addresses the challenges in meeting the high distillate demands while maintaining key product quality specifications. We explore the impact of refinery processes such as hydrotreating, hydrocracking and hydrodewaxing on product yields and cycle life. We also evaluate the impact of varying feedstocks on the middle distillate yields and quality. Two Companies Joined to Develop a Catalytic Solution for Bottoms Upgrading to Diesel in the FCC Unit By William Morales, Hipólito Rodríguez, Luis Javier Hoyos, Tania Chanaga, Luis Almanza, Ecopetrol - Instituto Colombiano de Petróleo Uriel Navarro, Larry Hunt, Clemencia Marín, Hongbo Ma, Rick Wormsbecher, Tom Habib, Grace Cayalysts Technologies Ecopetrol (Colombia) and W.R. Grace joined to develop a new catalyst technology geared towards increasing bottoms cracking to produce more diesel in efforts to meet local and worldwide demands. The project included intensive Pilot Plant work (DCR), with the implementation of existing and new deactivation techniques for catalyst, and a commercial trial of the new catalyst technology in an Ecopetrol FCC. Meeting Tier 3 Gasoline Sulfur Regulations New Tier 3 gasoline regulations require <10 ppm sulfur in the gasoline compared to 30 ppm in Tier 2. The options for accomplishing this usually involve some form of hydrotreating before or after the FCC. There are several catalyst options and operating strategies that will produce a reduction in gasoline sulfur, while minimizing the detrimental effects normally associated with some of these solutions. Catalagram ISSUE 114, Spring 2014 Editor: Rosann Schiller Contributors: Luis Almanza Colin Baillie Kenneth Bryden Tania Chanaga Michael Federspiel E. Tom Habib, Jr John Haley Luis Javier Hoyos Larry Hunt Jeff Koebel Hongbo Ma Clemencia Marín William Morales Uriel Navarro Charles Olsen Hipólito Rodríguez Greg Rosinski Rosann Schiller Brian Watkins Rick Wormsbecher Please address your comments to: betsy.mettee@grace.com Grace Catalysts Technologies 7500 Grace Drive Columbia, MD W. R. Grace & Co.-Conn

4 Editorial Dear Refiners, When a freshly minted journalism major arrived at Grace 40 years ago, she knew nothing about oil refining. She was handed a stack of Catalagrams (already in its 15th year) and the only thing she understood was a line in one of the past editorials that quoted from an old Art Linkletter show, Kids say the Darndest Things : Linkletter: Do you know what a cat cracker is? Boy: (shrugging) I dunno maybe a cat who eats crackers? Jeff Hazle, AFPM Technical Director, presents the author with the Peter G. Andrews Lifetime Achievement Award at the 2008 Question and Answer Session. This journalism major has become pretty familiar with what a cat cracker is since then. Many things have changed in refining since 1974, but two things will always be true: -The refiner s need to get the optimal value out of a barrel of oil -Grace and ART s commitment to achieving that goal Over those 40 years, I ve seen refining become more exact and challenging. And, always we ve responded, whether it s broadening our product portfolios, strengthening our industry-leading tech service, investing in our plants, committing to R&D, or expanding globally to meet market demand. I m proud and privileged to have worked with my ART and Grace colleagues and the fine people in the petroleum refining industry and I am confident in our joint future. Sincerely, Elizabeth W. Mettee Director of Communications Grace Catalysts Technologies Advanced Refining Technologies 2 Issue No. 114 / 2014

5 Processing Tight Oils in FCC: Issues, Opportunities and Flexible Catalytic Solutions Kenneth Bryden Manager, FCC Evaluations Research Michael Federspiel National Sales Leader, Americas E. Thomas Habib, Jr. Director, Customer Research Partnerships and DCR Licensing Manager Rosann Schiller Marketing Director, FCC Commercial Strategy Grace Catalysts Technologies Columbia, MD, USA Abstract Tight oils (also called shale oils) such as Eagle Ford and Bakken are fast becoming a major feed source for North American refineries. While these feedstocks are generally light and sweet, issues that refiners can face when processing tight oil include: contaminant metals, heat balance effects, and configurational imbalances in the refinery. This paper provides detailed characterization of tight oils along with data on the cracking of these feedstocks under different operating conditions. Catalytic solutions for (1) metals tolerance, (2) achieving maximum conversion and selectivity on light feeds, and (3) optimum butylene selectivity, are discussed, along with case studies on how refiners can apply new catalyst technologies to maximize the value present in tight oil feedstocks. Introduction As novel technology for hydraulic fracturing with directional drilling continues to develop, tight oil (also called shale oil) will continue to be a game changer for North American refiners. Although credited with many advantages, tight oil does not come without its challenges. Suppliers and processors alike are urgently working to adapt to the changing oil landscape. Just a few years ago, investments were focused on processing heavy crudes. Now, however, the industry is faced with lighter, sweeter crude streams from tight oil plays. In varying degrees at each refinery, tight oil makes up only a percentage of the total feedstock. In December 2013, production from the Bakken region passed 1.0 MM bbl/day and production from the Eagle Ford region reached an estimated 1.23 MM bbl/day 1. The December 2013 production of these two tight oil regions is slightly more than 10% of the total US crude oil demand. The percentage of tight oil could grow substantially as tight oil production increases and refiners invest in process modifications to handle this lighter feed. While drilling technology advances and the rapid growth of tight oil production have made forecasts difficult, the U.S. Energy Information Agency currently forecasts that United States tight oil production will top 4.8 MM bbl/day in Tight oil resources are not confined to the United States. Recent analysis indicates that tight oil formations are located throughout the world and constitute a substantial share of overall global technically recoverable oil resources 3. The January 2014 BP Energy Grace Catalysts Technologies Catalagram 3

6 Outlook projects that by 2035 tight oils will constitute 7% of the total global oil supply, with more than one third of tight oil production coming from outside the United States 4. While the North American refining industry undergoes a renaissance due to abundant tight oil, the new feeds present challenges as well as opportunities. This paper discusses the challenges with tight oil feeds and how to overcome them with proper choice of catalyst technology. Tight Oil Properties Tight oil is highly variable. Density and other properties can show wide variation, even within the same field 5-8. Tight oils are generally light, paraffinic and sweet. Table I presents the properties of a sample of whole Bakken crude, compared to publically published assays of Bakken, West Texas Intermediate (WTI) and Light Louisiana Sweet (LLS) and a typical Eagle Ford crude based on the Eagle Ford Marker. Eagle Ford crude is highly variable and the Eagle Ford Marker is based on a pool of Eagle Ford assays 10. The Bakken crude is light and sweet with an API of 42 and a sulfur content of 0.19 wt.%. Similarly, Eagle Ford is a light sweet feed, with a sulfur content of ~0.1 wt.% and with published APIs between 40 API and 62 API, with a value of 47 used for the Eagle Ford Marker. Similar to other light crudes, raw Bakken crude and Eagle Ford crude have a low amount of FCC feed (<28% 680 F+ for Bakken, and <27% 680 F+ for Eagle Ford Marker). The straight run Bakken sample was distilled into a 430 F minus gasoline cut and a 430 F to 650 F LCO cut and the properties of these cuts were measured to better characterize the Bakken feed. The gasoline composition and properties were analyzed via a Grace s proprietary G-Con octane calculation software based on detailed GC analysis 12,13. The gasoline fraction from the straight Bakken was highly paraffinic and had low octane numbers (a RON of 61 and MON of 58). The LCO fraction had an aniline point of 156 F and an API gravity of 37.6, resulting in a diesel index of 59. Table II presents properties of a 430 F+ distillation of Bakken, a 650 F+ distillation of Bakken, along with two Eagle Ford based FIGURE 1: Scanning Electron Micrograph of Sediment Filtered from Whole Bakken Crude (pg. 6) 4 Issue No. 114 / 2014

7 Bakken sample used in this work Published Assay Data Bakken (9) WTI (9) LLS (9) Typical Eagle Ford (10, 11) API Gravity Degrees 41.9 > Sulfur Wt.% 0.19 < Distillation Yield Wt.% Vol.% Vol.% Vol.% Vol.% Light Ends C1-C Naphtha C5-330 F Kerosene F Diesel F Vacuum Gas Oil F Vacuum Residue F Total Conradson Carbon Residue Gasoline Fraction Properties LCO Fraction (430 F-650 F) Properties Wt.% 0.78 RON (G-Con) 60.6 MON (G-Con) 57.6 Anline Point, F API Gravity 37.6 Diesel Index 58.6 TABLE I: Properties of Straight Run Tight Oil Feed Used in this Study Compared to Publically Published Assay Data Property Eagle Ford Condensate Splitter Bottoms HVGO Derived from 85% Eagle Ford 430 F+ Distillation of Whole Bakken Crude 650 F+ Distillation of Whole Bakken Crude Mid-Continent VGO API Gravity, F CCR, wt.% K Factor Sulfur, wt.% Basic Nitrogen, wt.% Hydrogen, wt.% Percent Boiling > 1000 F Molecular Weight n-d-m Analysis Ca, Aromatic Ring Carbons, % Cn, Naphthenic Ring Carbons, % Cp, Paraffinic Carbons, % D2887 Simulated Distillation, F Initial Boiling Point % % % % % % % % % TABLE II: Properties of Tight Oil Derived FCC Feeds Compared to Typical Mid-Continent Vacuum Gas Oil Grace Catalysts Technologies Catalagram 5

8 Eagle Ford Condensate Splitter Bottoms 650 F+ Distillation of Whole Bakken Crude Mid-Continent VGO Saturates AVE, wt.% AVE, wt.% AVE, wt.% C(N)H(2N+2) Paraffins C(N)H(2N) Monocycloparaffins C(N)H(2N-2) Dicycloparaffins C(N)H(2N-4) Tricycloparaffins C(N)H(2N-6) Tetracycloparaffins C(N)H(2N-8) Pentacycloparaffins Total Saturates Monoaromatics C(N)H(2N-6) Alkylbenzenes C(N)H(2N-8) Benzocycloparaffins C(N)H(2N-10) Benzodicycloparaffins Diaromatics C(N)H(2N-12) Naphthalenes C(N)H(2N-14) C(N)H(2N-16) Triaromatics C(N)H(2N-18) C(N)H(2N-22) Tetra-aromatics C(N)H(2N-24) C(N)H(2N-28) Total Aromatics Thiophenic Compounds C(N)H(2N-4)S Thiophenes C(N)H(2N-10)S Benzothiophenes C(N)H(2N-16)S Dibenzothiophenes C(N)H(2N-22)S Naphthobenzothiophenes Total Thiophenic Compounds TABLE III: HRMS 22-Component Hydrocarbon Types Analysis of Two Tight Oil Derived FCC Feeds Compared to a Typical Mid-Continent Vacuum Gas Oil fluid catalytic cracking (FCC) feeds. A typical mid-continent VGO is included for comparison. The tight oil derived feeds are all light and paraffinic. Table III shows the results of an HRMS 22- Component Hydrocarbon Types Analysis of the FCC feeds. This breakdown of hydrocarbon types further highlights that the Bakken and Eagle Ford crudes are high in saturates. However, the 650 F+ distillation of the Bakken crude does contain a significant portion of tetra-aromatics that are inactive to cracking and are coke precursors. While most tight oils are low in nickel and vanadium, they have been found to be high in inorganic solids, iron, and alkali metals 6,14. Table IV presents metals analysis of several tight oil derived feed streams along with published metals analyses of tight oil. While metals levels in the samples vary (as would be expected for tight oil), iron and calcium levels are generally high. Reports from the field indicate that Bakken crude is typically low in nickel and vanadium, while crudes sourced from the Eagle Ford formation have higher nickel and vanadium levels that can vary significantly based on their source. To better understand the possible sources of metals in tight oil, a sample of whole Bakken crude was filtered through a 0.8 micron filter and the solids recovered. Scanning electron microscopy of the solids identified irregular micron and submicron sized particles as shown in Figure 1 (pg.4). Energy dispersive spectroscopy maps of iron, sulfur and calcium are pictured in Figure 2. The iron in the sediments is associated with the sulfur. 6 Issue No. 114 / 2014

9 FIGURE 2: Energy Dispersive Spectroscopy Maps of Sediment in Bakken Crude X-ray diffraction of the sediment identified the following crystalline phases: anhydrite (Ca 2 SO 4 ), magnetite (Fe 3 O 4 ), and pyrrhotite (substoichiometric FeS). Anhydrite and pyrrhotite have been mentioned in the literature as being present in the Bakken formation 15,16. Based on this analysis, it appears that much of the iron in the Bakken crude comes from very small particles of iron oxide and pyrrhotite. Cracking Yields of Whole Tight Oil and Tight Oil Cuts To examine the impact of tight oil on FCC yields, cracking was done with whole Bakken, a 430 F+ distillation of Bakken, a 650 F+ distillation of Bakken, two Eagle Ford derived FCC feeds, and a reference sample of a typical mid-continent VGO. Feed properties Property Mid- Continent VGO Samples in this Paper Published Assay Data 14 Published Assay Data 7 Whole Bakken Crude 650 F+ Distillation of Bakken Crude Eagle Ford Condensate Splitter Bottoms Barium, ppm < Flashed Bakken Crude not reported 75% Eagle Ford Stream (total) not reported 75% Eagle Ford Stream (filtered) not reported Bakken Crude Eagle Ford Crude Calcium, ppm < Iron, ppm < Magnesium, ppm < < < Nickel, ppm < <0.14 Potassium, ppm < < < Sodium,ppm < Vanadium, ppm < <0.05 TABLE IV: Metals Analysis of Several Tight Oils Grace Catalysts Technologies Catalagram 7

10 Total Surface Area, m 2 /g 196 Zeolite Surface Area, m 2 /g 110 Matrix Surface Area, m 2 /g 86 Unit Cell Size, Å Rare earth, wt.% 2.1 Alumina, wt.% 52.1 TABLE V: Deactivated Catalyst Properties are presented in Tables I and II. Cracking was done over an FCC catalyst in a fixed-fluidized bed ACE test unit 17 at a constant reactor temperature of 980 F, using three catalyst-to-oil ratios (4,6,8) for each of the feeds. The catalyst used in the experiments was an FCC catalyst with optimized matrix and mesoporosity, deactivated metals free using a CPS type protocol. The properties of the deactivated catalyst are given in Table V. Interpolated yields at a catalyst-to-oil (C/O) ratio of 6 are presented in Table VI. The whole Bakken crude resulted in low coke, and a low octane gasoline. While the whole Bakken crude yielded significant gasoline, much of the gasoline was from uncracked starting material in the feed. The yields of the 430 F+ and 650 F+ distillations of the Bakken crude were similar to those of the mid-continent VGO reference sample. The 650 F+ distillation of the whole Bakken crude had higher coke than the mid-continent VGO due to its heavier end as seen it its higher Conradson carbon number and higher tetra-aromatic content. Compared to the mid-continent VGO, the light Eagle Ford derived feeds yielded higher gasoline and lower coke, bottoms and LCO. Processing Straight Run Tight Oil - Effect of Operating Variables on Yields and Product Properties While fluid catalytic cracking is typically done to reduce the molecular weight of the heavy fractions of crude oil (such as vacuum gas oil and atmospheric tower bottoms), in some cases refiners are charging whole tight oil as a fraction of their FCC feed. Since tight oil is low in components boiling above 650 F and high in components boiling below 650 F, a refiner processing 100% tight oil can be at their maximum distillation and light cut capacity and be short on FCC feed. Also, whole crude oil has been charged to FCC units when gas oil feed is not available due to maintenance on other units in the refinery 18, and to produce a low-sulfur synthetic crude 19. As a model case to understand the cracking of whole crude oil in the FCC and the effect of process conditions on yields, the whole Bakken crude described in Table I was processed in a DCR circulating riser FCC pilot plant at three riser outlet temperatures: 970 F, 935 F, and 900 F. As a reference case, the mid-continent VGO described in Table II was cracked at a riser outlet temperature of 970 F. Details of the DCR circulating riser pilot plant can be found in Reference 20. The catalyst used in the experiments was a high-matrix FCC catalyst, deactivated metals free using a CPS type protocol. The properties of the deactivated catalyst are given in Table V. Figure 3 presents the yield structure of the starting feeds and the cracked products for a riser outlet temperature of 970 F. The midcontinent VGO is a typical VGO feed with a large portion of 650 F+ Whole Bakken Crude 430 F+ Distillation of Bakken 650 F+ Distillation of Bakken Mid-Continent VGO HVGO Derived from 85% Eagle Ford Eagle Ford Condensate Splitter Bottoms Conversion, wt.% H 2 Yield, wt.% C 1 's+c 2 's, wt.% Total C 3, wt.% C 3 =, wt.% Total C 4 's, wt.% C 4 =, wt.% LPG, wt.% Gasoline (C F), wt.% RON (G-Con) MON (G-Con) LCO ( F), wt.% Bottoms (700 F+), wt.% Coke, wt.% TABLE VI: Interpolated Yields at C/O = 6 for Five Tight Oil Derived Feedstocks Compared to Mid-Continent VGO 8 Issue No. 114 / 2014

11 Wt.% Fresh Feed Straight Run Bakken Bakken Cracked at 970 F ROT Mid-Continent VGO Cracked at 970 F Mid-Continent VGO Dry Gas LPG Gasoline (C F) LCO ( F) Bottoms (650 F+) Coke FIGURE 3: DCR Yield Structure of Starting Feeds and Cracked Products for Straight Run Bakken and Mid-Continent VGO (970 F Riser Outlet Temperature) material and small fraction of LCO range material. When cracked, the LCO range material cracks to LPG and gasoline, and the 650 F+ material cracks to the typical distribution of LPG, gasoline and LCO, resulting in a net increase in LCO. The whole Bakken crude starts with large fractions of gasoline and LCO range material and a low amount of 650 F+ material. The amount of gasoline produced after cracking is high since the LCO range material cracks to predominantly gasoline and much of the starting gasoline is unconverted. LCO yields are low since there is little starting 650 F+ material to crack to LCO. For the three different reactor outlet temperatures, plots of catalyst-to-oil ratio, gasoline, LCO, and coke yields versus conversion are shown in Figure 4. As expected, lowering reactor temperature increases the amount of LCO produced. Cracking straight run tight oil produces little coke and bottoms. At the same conversion level, lowering reactor temperature results in slightly more gasoline yield (due to increased C/O), which is consistent with prior work 21. At a riser outlet temperature of 970 F, the whole Bakken feed produces more gasoline, less LCO and less coke than the reference mid-continent VGO. Figure 5 presents plots of gasoline olefins, iso-paraffins and RON and MON estimated via G-Con. Cracking straight run Bakken tight oil produces a paraffinic low-quality gasoline with research octane less than 80 and motor octane less than 70. At constant conversion, increasing reactor temperature results in more gasoline olefins and higher research octane number. 10 C/O Ratio 70 C 5 + Gasoline, wt.% Bakken 900 F 20.0 LCO ( F), wt.% 50 4 Coke, wt.% Bakken 935 F Bakken 970 F VGO 970 F Conversion, wt.% FIGURE 4: Product Yields as a Function of Riser Outlet Temperature and Feed Grace Catalysts Technologies Catalagram 9

12 95 G-Con RON EST 80 G-Con MON EST Bakken 900 F 35 G-Con O, wt.% G-Con I, wt.% Bakken 935 F Bakken 970 F VGO 970 F Conversion, wt.% FIGURE 5: Gasoline Properties as a Function of Riser Outlet Temperature and Feed 22 LCO ( F), wt.% 50 Diesel Index Bakken 900 F Bakken 935 F Bakken 970 F VGO 970 F Conversion, wt.% FIGURE 6: Effect of Conversion Level and Feed Type on LCO Yield and Quality 10 Issue No. 114 / 2014

13 Diesel quality is of great interest to refiners. Synthetic crude produced in the circulating riser pilot plant runs was distilled to recover the 430 F to 650 F LCO fraction. Aniline point and API gravity of the LCO were then measured to allow calculation of the diesel index, a measure of LCO quality [diesel index = (aniline point x API Gravity)/100]. Figure 6 presents data for LCO yield and LCO quality as a function of conversion. As seen in the data, increasing conversion lowers LCO quality as a result of increased cracking of the LCO range paraffins to lighter hydrocarbons. As seen in prior work 22, LCO quality follows LCO yield and did not appear to be influenced by reactor temperature at constant conversion. Diesel index values of the LCO produced by cracking whole tight oil were significantly higher than those obtained when cracking the reference mid-continent VGO. At a conversion of 78 wt%, the whole Bakken gave a LCO with a diesel index of 40, compared to a diesel index of 10 obtained for the LCO produced from the mid-continent VGO. This study of the effect of operating variables shows that whole shale oil responds to FCC operating conditions similarly to conventional oils. However, the product yield slate is substantially different in that good quality (high diesel index) LCO is produced in the FCC and large amounts of low octane gasoline are made. Processing Challenges Light sweet crudes are generally easy to process, although challenges arise when these crudes are the predominant feedstock in refineries designed for heavier crudes. Tight oils, like other light sweet crudes, have a much higher ratio of 650 F- to 650 F+ material when compared to conventional crudes. Bakken tight oil has a nearly 2:1 ratio, while typical crudes such as Arabian Light, have ratios near 1:1. A refinery running high percentages of tight oil could become overloaded with light cuts, including reformer feed and isomerization feed, while at the same time short on feed for the fluid catalytic cracking unit (FCCU) and the coker. Many refiners report that while they are benefitting from favorable crude prices they often are struggling to keep downstream process units full. At low FCC utilization rates, oftentimes the alkylation unit is unconstrained, leading to an octane shortage. Unconstrained downstream units are just one of the challenges faced by North American refiners. Unconventional oils can vary wildly in composition from cargo to cargo. Receiving crude in batches via rail, truck or barge can result in FCC feed changing rapidly over the course of several weeks or several days. To increase utilization rates, heavier crudes may be blended with lighter tight oils, resulting in a barbell crude, which has a lot of material boiling at each end of the boiling point curve, but little in the middle, reducing VGO yield for the FCC. As previously discussed, some refiners have tried charging whole crude to the FCCU in order to boost utilizations, to the detriment of other key yields such as FCC naphtha octane. At the FCCU, the challenges range from difficulty maintaining heat balance when the feed is very light, to unexpected coke make when contaminant metals rise rapidly. When operating with highly paraffinic light tight oil feeds that crack easily and produce little coke, the FCC may become circulation constrained due to low regenerator temperatures. Refiners report spikes of both conventional (sodium, nickel and vanadium) and unconventional metals (iron and calcium) when running tight oil derived feeds. Sodium and vanadium deactivate zeolite and suppress activity; nickel promotes dehydrogenation reactions, leading to high gas make. Unconventional metals such as iron and calcium deposit on the catalyst surface and cause a loss of diffusivity, which leads to a loss in conversion and an increase in coke and bottoms. To maximize profitability with rapidly changing feed quality, catalyst flexibility is key. Catalytic Solutions Flexible catalyst functionality is critical for processing unconventional feeds and mitigating the associated processing challenges. Grace s newest FCC catalyst family, that of ACHIEVE catalysts, is designed to provide refiners that flexibility. Figure 7 summarizes the challenges posed by tight oils and the catalyst technology solutions for mitigating them. ACHIEVE features an optimized matrix technology to provide coke-selective bottoms conversion without a gas penalty. The technology in the high diffusivity matrix of the ACHIEVE catalyst is based on technology embodied in the popular MIDAS catalyst, which has been commercially proven to be more iron tolerant than competitive offerings. ACHIEVE incorporates best-in-industry metals traps for nickel and vanadium, which are highly effective to minimize coke and gas formation from these conventional metals. ACHIEVE FCC catalyst also contains ultra-stable zeolite that retains activity in the face of contaminant metals spikes. ACHIEVE can be formulated over a range of activity, rare-earth exchange, and isomerization activities, to deliver an optimal balance of gasoline yield to LPG while maintaining an optimum level of butylenes for the alkylation unit. Increasing catalyst activity, via zeolite or rare-earth exchange can alleviate a circulation constraint and restore the heat balance to a comfortable level. ZSM-5 based additives can be used to boost octane, but the associated yield of propylene is not always desirable. A better solution is to boost zeolite isomerization activity within the catalyst to selectively increase the yield of FCC butylene and iso-butane, keeping the alky unit full and maintaining refinery pool octane. The following examples illustrate how the flexibility of the ACHIEVE catalyst family can address the challenges posed by tight oil. Grace Catalysts Technologies Catalagram 11

14 Challenge Consequence Catalyst Solution Fe and Ca Poisoning Unpredictable Swings in Contaminant Metals FCC Heat Balance Refinery Imbalances Loss of Bottoms Cracking and Conversion Loss of Surface Area Leads to Lower MAT and Conversion Low Regenerator Temps, Circulation Constraints Lower Severity to Control LPG Reduces Octane Employ a High Porosity Matrix Utilize Traps for Ni and V with High Stability Zeolites Increase Catalyst Activity Boost Zeolite Isomerization Activity FIGURE 7: Challenges Posed by Tight Oil Feedstocks, Their Consequences, and the Catalytic Solutions Iron and Calcium Tolerance Iron and calcium have a negative effect on catalyst performance. While particulate tramp iron from rusting refinery equipment does not have a significant detrimental effect on catalyst, finely dispersed iron particles in feed (either as organic compounds or as colloidal inorganic particles) can deposit on the catalyst surface, reducing its effectiveness 23,24. The iron deposits combine with silica, calcium, sodium and other contaminants to form low melting temperature phases, which collapse the pore structure of the exterior surface, blocking feed molecules from entering the catalyst particle and reducing conversion 25. Iron in combination with calcium and/or sodium has a greater negative effect on catalyst performance than iron alone. The symptoms of iron and calcium poisoning include a loss of bottoms cracking, as feed particles are blocked from entering the catalyst particle, and a drop in conversion. Catalyst design can be optimized to resist the effects of contaminant iron and calcium in tight oil feedstocks. High alumina catalyst, especially catalyst with alumina-based binders and matrices, such as Grace s MIDAS catalyst, are best suited to process iron- and calcium-containing feeds due to their resistance to the formation of low-melting-point phases that destroy the surface pore structure 26. Optimum distribution of mesoporosity also plays a role in maintaining performance because diffusion to active sites remains unhindered, despite high-contaminant metals. The resistance of MIDAS catalyst to iron and calcium poisoning has been demonstrated in many commercial applications 26,27. Figure 8 presents data from the application of Grace s MIDAS 638 catalyst in an operation running 100% tight oil and high levels of iron. The switch to MIDAS 638 catalyst reduced bottoms yield even when iron contamination increased ECAT Fe, wt% Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar Bottoms Yield, wt% Apr-12 Jul-12 Nov-12 Mar-13 Jul-13 Nov-13 Mar-14 Base MIDAS 638 FIGURE 8: MIDAS 638 Catalyst Maintains Selectivity in 100% Tight Oil Operation 12 Issue No. 114 / 2014

15 Nickel and Vanadium Tolerance Grace has a long history of incorporating both nickel and vanadium metals trapping into the catalyst system, mitigating the negative impacts of the metals. Nickel is trapped where it is initially cracked onto the catalyst with a proprietary Grace alumina. The alumina absorbs the nickel into the catalyst particle, forming a stable nickel aluminate that is no longer active for dehydrogenation reactions. Grace has been highly successfully in utilizing this technique. Currently 65+% of our worldwide customers are taking advantage of this technology. For vanadium trapping, incorporation of a trap in the catalyst system can provide widely dispersed trapping capability, more effectively reducing the negative impacts of the contaminant. Grace s IVT-4 is an integral rare-earth based vanadium trap that converts contaminant vanadium into an inert rare-earth vanadate, greatly reducing zeolite deactivation and coke and gas production. Grace is currently using IVT-4 in 60%+ of our worldwide catalyst formulations. An example of the excellent metals trapping performance of the ACHIEVE catalyst system is shown in Figure 9, which plots Ecat selectivities of ACHIEVE catalyst versus a competitive base. The refiner was processing tight oil along with a shifting mix of opportunity crudes and needed a catalyst with better metals tolerance. At the same Ecat nickel equivalents, the ACHIEVE catalyst resulted in lower coke, lower gas and lower hydrogen than the competitive base. Figure 10 presents box plots based on refinery operating data from the reformulation showing that ACHIEVE catalyst resulted in higher gasoline yields and lower hydrogen, delta coke and slurry yield. The superior metals tolerance of the ACHIEVE catalyst allowed the refiner to increase conversion without increasing catalyst addition rate. The changes in operating conditions and yields after moving to ACHIEVE catalyst are summarized in Table VII. Applying typical Gulf Coast economics, the increase in gasoline yield and drop in slurry resulted in a benefit of ~$0.70/bbl for the refinery. Maintaining Heat Balance When processing very light tight oil derived feedstocks, insufficient catalytic activity requires that the catalyst circulation rate increase so that conversion, and thus the coke yield from the catalyst, increases to satisfy the FCC heat balance. If the FCCU cannot physically circulate enough catalyst, it will be necessary to either reduce the unit charge rate or the reaction severity to stay within the FCC catalyst circulation limit. Alternatively, refiners can satisfy the heat balance by blending in a heavier feedstock, recycling slurry, burning torch oil, increasing regenerator air preheat, or 2.0 Coke Factor 6 Gas Factor H 2 Yield, SCFB Competitive Base ACHIEVE TM Catalyst Ecat Ni Equivalents, ppm FIGURE 9: ACHIEVE Catalyst Delivers Superior Metals Tolerance Compared to a Competitive Base Grace Catalysts Technologies Catalagram 13

16 Hydrogen, SCFB Conversion, vol.% Gasoline, vol.% Gasoline + LCO, vol.% Slurry, vol.% Delta Coke Competitive Base ACHIEVE TM Catalyst Competitive Base ACHIEVE TM Catalyst Competitive Base ACHIEVE TM Catalyst FIGURE 10: Unit Data Demonstrating Improved Performance of ACHIEVE Catalyst Versus the Competitive Base Operating Parameters Delta (ACHIEVE - Competitive Base) Relative Fresh Feed Rate -4% Feed Temp, F Feed API Reactor Temp, F Regen Dense, F Regen Dilute, F Catalyst Additions, lbs/bbl Yields -72 F Same +6 F -1 F +3 F Same Coke, wt.% +0.1 Delta Coke, wt.% F Conversion, vol.% +3.8 H 2, SCFB -20 Dry Gas, vol.% Same C 3, vol.% +1.2 C 4, vol.% +1.4 Gasoline, vol.% +2.1 LCO, vol.% -1.7 Slurry Yield, vol.% -2.1 derating the stripping steam. However, these options often have a detrimental effect on the operation 28,29. Table VIII summarizes the operating changes that can be made to maintain heat balance and the potential issues of each change. The best way to satisfy the heat balance with a very light feedstock is via proper application of catalyst technology. As an example of the role of catalyst activity in maintaining heat balance, consider an FCC unit operating on standard VGO that is contemplating a move to lighter tight oil feed type. Figure 11 presents pilot plant data of catalyst-to-oil ratio as a function of coke and conversion on the two feedstocks. The base case catalytic coke of 2.5 wt.% requires a C/O of about 5.5 and results in 74% conversion. In order to keep the 2.5% coke yield with the lighter tight oil feed, a C/O ratio of over 8.0 is necessary with an increase in conversion to about 77%. Most FCC units are not capable of this dramatic increase in the catalyst circulation rate and the catalyst circulation hydraulics will likely limit the unit severity or throughput. TABLE VII: ACHIEVE Yield Shifts Deliver$0.70/BBL Benefit 14 Issue No. 114 / 2014

17 Cat-to-Oil Ratio Coke, wt.% Base - VGO Feed Conversion, wt.% Light Tight Oil Feed FIGURE 11: C/O Ratio Must Increase to Satisfy Heat Balance, After Shift to Light Tight Oil Option Blend in heavier feedstock Potential Issues Availability of heavier feedstock. Crude incompatibility and asphaltene precipitation. High metals in heavier crudes. Increase feed preheat Increased energy consumption. Metallurgical limits. Increase in non-selective thermal cracking and dry gas production. Slurry recycle Feed system fouling. Catalyst erosion. Increased dry gas yield. Burning torch oil in the regenerator Accelerated catalyst deactivation. Burning of a high value stream. Reduce stripping steam rate Wear of stripper steam rings. Stripper steam plugging. Accelerated catalyst deactivation. Increase preheat of regenerator air Increased catalyst and air grid nozzle attrition. Increase FCC catalyst activity Best and most profitable option for maintaining heat balance. TABLE VIII: Options for Maintaining Heat Balance with Light Feeds Grace Catalysts Technologies Catalagram 15

18 Cat-to-Oil Ratio Coke, wt.% Conversion, wt.% Base - VGO Feed Light Tight Oil Feed Catalyst A FIGURE 12: Effect of Change in Catalyst Activity on Catalyst to Oil Requirements to Maintain Constant Coke In this same example, we consider a catalyst reformulation to a more active catalyst with a different coke to conversion relationship as seen in Figure 12. Here, Catalyst A is applied and a much more modest C/O of 6.5 is required to satisfy the coke yield, due to the inherent catalyst activity of Catalyst A. Because of the coke to conversion relationship of Catalyst A, higher conversion is achieved. Using a high activity catalyst is required to counter the effects of low delta coke, but it is important to select a catalyst with the proper coke selectivity (coke to conversion relationship). ACHIEVE catalyst can be formulated with ultra-high activity zeolite to counter the effects of low delta coke, while delivering the proper coke selectivity. Grace has had multiple experiences with reformulations for processing lighter feeds from tight oil or traditional hydrotreated FCC feed. In one commercial application, a refiner switched from a competitive catalyst designed for high activity to Grace s ACHIEVE catalyst. Feed and catalyst properties are presented in Table IX. The feed was light and paraffinic with an API of Table X presents yields at constant conversion based on testing of feed and equilibrium catalyst from the unit. At constant conversion, the switch to ACHIEVE catalyst resulted in higher activity, higher gasoline, higher LCO, lower bottoms, and improved coke selectivity. Table XI presents yields at constant coke. At constant coke, the switch to ACHIEVE catalyst resulted in higher activity, higher gasoline and lower bottoms and an economic uplift of ~$0.40/bbl. Maintaining Refinery Pool Octane A common challenge reported by refiners operating on unconventional feeds, such as shale or tight oil, is a loss of gasoline pool octane, caused by reduced volume of alkylation feedstock. Within the ACHIEVE catalyst family, ACHIEVE 400 catalyst is formulated with multiple zeolites with tailored acidity, to deliver an optimum level of butylenes to keep the alkylation unit full and maintain refinery pool octane. Incorporation of isomerization activity into the catalyst particle itself results in a more desirable yield pattern than would be realized by use of a traditional octane boosting FCC additive. In addition, ACHIEVE 400 has been shown to increase the octane of FCC naphtha. An example of the yield shifts that are possible with this technology is found in Table XII, which presents yields based on DCR pilot plant testing of base MIDAS catalyst, MIDAS catalyst with added conventional ZSM-5 based OlefinsMax additive, and ACHIEVE 400 catalyst with multiple zeolite technology. The physical properties of the fresh catalysts in the study are given in Table XIII. With traditional ZSM-5 technology, cracking of gasoline olefins continues past C 7 into the C 6 and generates a disproportionate amount of propylene relative to butylenes as shown in Figure 13. Figure 14 presents the difference in olefins yields by carbon number versus the base case for the ACHIEVE catalyst and the MIDAS catalyst with OlefinsMax additive. Olefins cracking for the ACHIEVE 400 catalyst stopped at C 7 olefins (as seen by the ACHIEVE 400 catalyst producing the same level of C 6 olefins as 16 Issue No. 114 / 2014

19 Feed Properties API Gravity, F 29.5 CCR, wt.% 0.29 K-factor n-d-m Analysis Ca, Aromatic Ring Carbons, % 13.9 Cn, Naphthenic Ring Carbons, % 16.9 Cp, Paraffinic Carbons, % 69.2 Equilibrium Catalyst Properties Competitive Base ACHIEVE TM Catalyst Zeolite Surface Area, m 2 /g Ni, ppm V, ppm TABLE IX: Feed and Catalyst Properties for Commercial Application of High Activity Catalyst with Light Feed Competitive Base ACHIEVE TM Catalyst C/O Ratio Conversion, wt.% H 2 Yield, wt.% Dry Gas, wt.% Propylene, wt.% Total C 3 's, wt.% Total C 4='s, wt.% Total C 4 's, wt.% Gasoline, wt.% LCO, wt.% Bottoms, wt.% Coke, wt.% TABLE X: ACHIEVE Catalyst Outperforms Competitive Technology in a Light Feed Application - Yields at Constant Conversion Competitive Base ACHIEVE TM Catalyst Coke, wt.% C/O Ratio Conversion, wt.% H 2 Yield, wt.% Dry Gas, wt.% Propylene, wt.% Total C 3 's, wt.% Total C 4='s, wt.% Total C 4 's, wt.% Gasoline, wt.% LCO, wt.% Bottoms, wt.% TABLE XI: ACHIEVE Catalyst Outperforms Competitive Technology in a Light Feed Application - Yields at Constant Coke Reactant C 8 = 2 C 4 = C 3 = + C 5 = Selectivity 44% 56% Relative Selectivity C 3 =/C 4 = ACHEIVE TM 400 Catalyst C 7 = C 3 = + C 4 = C 2 = + C 5 = 95% 2% ZSM-5 Additive C 6 = 2 C 3 = C 2 = + C 4 = 83% 16% Buchanan, et. al., Ref. 30 FIGURE 13: ACHIEVE 400 Catalyst Preferentially Cracks Gasoline Olefins at C 7 and Above Grace Catalysts Technologies Catalagram 17

20 Olefins, wt.% FF Base MIDAS Catalyst + OlefinsMax Additive Carbon Number ACHIEVE TM 400 Catalyst FIGURE 14: Incremental Olefin Yields by Carbon Number at Constant Conversion Demonstrate that ACHIEVE 400 Catalyst Does Not Crack C 6 Olefins as ZSM-5 Based Additives Do 1.4 MON RON Conversion, wt.% Conversion, wt.% C4= Base MIDAS Catalyst Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst 0.8 FIGURE 16: ACHIEVE Delivers Higher RON and MON C 3 = Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst FIGURE 15: At Constant Conversion ACHIEVE 400 Delivers a Higher Ratio of C 4 to C 3 Olefins than Use of a Separate ZSM-5 Based Olefins Additive the base case), while the use of ZSM-5 additive resulted in cracking of C 6 olefins, as seen by the drop relative to the base case. The newly developed dual-zeolite technology in ACHIEVE 400 works synergistically with Grace s high diffusivity matrix, to selectively enhance olefinicity, preferentially cracking gasoline olefins at C 7 and above into butylene. The result is a higher ratio of C 4 to C 3 olefin yield than separate light olefins additives. Figure 15 illustrates the butylene selectivity improvement of ACHIEVE 400 catalyst compared to a system using conventional ZSM-5 based additive. At constant conversion, ACHIEVE 400 catalyst delivers higher gasoline octane and higher LPG olefins, with preferentially more butylenes over propylene. The net result is higher total octane barrels for the refinery. Figure 16 presents plots of RON and MON versus conversion, showing that the ACHIEVE 400 catalyst results in higher gasoline octane than the base MIDAS catalyst and the MIDAS catalyst with added conventional ZSM-5 based OlefinsMax additive. As seen in Figure 17, coke and bottoms are equivalent between the base case and the ACHIEVE 400 catalyst, demonstrating that the increased butylenes selectivity was realized without compromising the bottoms conversion activity of the catalyst. The distribution between different butylene isomers is the same with ACHIEVE 400 catalyst as with the MIDAS catalyst with added conventional ZSM-5 based OlefinsMax additive, as seen in Figure Issue No. 114 / 2014

21 Bottoms, wt.% Base MIDAS Catalyst Coke, wt.% 7.0 Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst FIGURE 17: Coke to Bottoms is Maintained with ACHIEVE 400 Catalyst 40% Motor Octane Number Research Octane Number Carbon Number Carbon Number Aromatics Olefins Naphthalenes monomethyl-iso-paraffins n-paraffins % Total C 4 = 30% 20% 10% FIGURE 19: Pure Component RON and MON as a Function of Hydrocarbon Type and Carbon Number (Based on API Research Project 45) 0% cc 4 = tc 4 = ic 4 = 1-C 4 = Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst FIGURE 18: Distribution of Butylene Isomers for ACHIEVE 400 and Base Midas + OlefinsMax The octane number of gasoline is determined by the hydrocarbon types present in the gasoline. While there are complex blending interactions between the different hydrocarbon types, the general effect of hydrocarbon type on octane can be seen in pure component octane data. Figure 19 presents pure component RON and MON values by carbon number for different hydrocarbon families based on data from API Technical Project In cases where more than one isomer is present, an average of the octane values for the different isomers was used. As seen in the figures, aromatics and olefins have roughly equivalent octanes, while naphthenes, iso-paraffins and normal paraffins have lower octane numbers. The octane numbers of olefins and aromatics are relatively unchanged with carbon number, while those of naphthenes, iso-paraffins and normal paraffins drop as the chain length grows. In addition to hydrocarbon type (olefin, paraffins, aromatic, etc.), the degree of branching within a molecule affects octane. As an example, for C 6 olefins, the straight chain molecule 1-hexene has a RON of 76, the single branched molecule 2- methyl-1-pentene has a RON of 94, and the doubly branched molecule 2,3-dimethyl-2-butene has a RON of The octane enhancement from the ACHIEVE 400 catalyst is from increased gasoline olefins and from increased olefins isomerization. In Table XII, the PIANO data shows that the ACHIEVE 400 catalyst has a higher olefins concentration in the gasoline than the MIDAS catalyst base case or the MIDAS catalyst with OlefinsMax additive. The degree of olefins branching of gasoline in the DCR study is presented in Figure 20. The gasoline olefins produced by the ACHIEVE 400 catalyst were more highly branched, resulting in higher naphtha octane. The increased butylene selectivity of ACHIEVE 400 catalyst can help refiners address the potential octane debits associated with light paraffinic tight oil feeds. Figure 21 presents plots of the annualized value of improved butylene selectivity for a 50,000 BBL/day FCCU based on several butylene to gasoline value differentials. For a hypothetical case where butylene is valued at $45/bbl over gasoline, each 0.1 wt.% increase in butylene selectivity results in >$0.8MM/yr more value. Grace Catalysts Technologies Catalagram 19

22 Base MIDAS Catalyst Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst Cat to Oil Dry Gas, wt.% C 3=, wt.% Total C 4 's, wt.% ic 4, wt.% nc 4, wt.% Total C 4=, wt.% C 4=/C 3=, wt.% Gasoline, wt.% LCO, wt.% Bottoms, wt.% Coke, wt.% G-Con RON G-Con MON G-Con P, wt.% G-Con I, wt.% G-Con A, wt.% G-Con N, wt.% G-Con O, wt.% TABLE XII: ACHIEVE 400 Catalyst Provides Higher Octane and More C 4 Olefins than Using ZSM-5 Additive Base MIDAS Catalyst Base MIDAS Catalyst + OlefinsMax Additive ACHIEVE TM 400 Catalyst Al 2 O 3, % RE 2 O 3, % ABD, g/cm APS, microns ZSA, m 2 /g MSA, m 2 /g TABLE XIII: Fresh Catalyst Properties Conclusion The tight oil boom has resulted in a renaissance in the North American refining industry. While tight oils are generally light and sweet and easy to crack, quality can vary greatly and tight oil derived feeds can contain sediments with high levels of iron and alkali metals. The light nature of these feeds can result in difficulty maintaining heat balance, and the paraffinic nature of the feed slate can result in octane debits in the refinery. Proper catalyst choice allows refiners to most fully exploit the opportunity of tight oil while minimizing the detrimental impacts. Grace s newest catalyst family, ACHIEVE catalyst, is designed with the flexibility to enable refiners to proactively respond to the opportunity of tight oil. The ACHIEVE catalyst family is currently in commercial testing. In addition to catalyst selection, an equally critical component to minimizing risks and challenges associated with processing unconventional feeds is solid technical service support. Grace has been providing industry-leading technical service to the refining industry since Grace retains qualified, experienced engineers to support FCC customers by providing application and operations expertise, as well as start-up and optimization assistance and industry benchmarking. With the backing of advanced R&D facilities and high throughput testing labs, let Grace s technical service team help you assess potential challenges before they occur in your FCCU via feed characterization, feed component modeling, and pilot plant studies. Understanding feed impacts earlier allows opportunity to optimize the operating parameters and catalyst management strategies, enabling a more stable and profitable operation. 20 Issue No. 114 / 2014

23 C5= Branched/C5 Total C6= Branched/C6 Total Base MIDAS Catalyst Acknowledgements The authors thank colleagues at Grace for assistance with the testing and analysis for this paper. The many contributions of Olivia Topete and Jeff Koebel to this paper are gratefully acknowledged. References Conversion, wt.% Conversion, wt.% Base MIDAS Catalyst + OlefinsMax Additive 1. U.S. Energy Information Administration, January 2014 Drilling Productivity Report for Key Tight Oil and Shale Gas Regions, released January 14, U.S. Energy Information Administration, Annual Energy Outlook 2014 Early Release Overview, December 16, U.S. Energy Information Administration, Technically Recoverable Shale Oil and Shale Gas Resources: An Assessment of 137 Shale Formations in 41 Countries Outside the United States, June BP, BP Energy Outlook 2035, January ACHIEVE TM 400 Catalyst FIGURE 20: ACHIEVE 400 Catalyst Results in Increased C 5 and C 6 Olefins Branching $6,000,000 $5,000,000 $4,000,000 $3,000,000 $2,000,000 $1,000, Uplift from Gasoline to C 4= (%) Value Differential between C 4= and Gasoline $60/BBL $45/BBL $30/BBL $15/BBL FIGURE 21: Annualized Value of Improved Butylene Selectivity for a 50,000 BBL/day FCCU 5. Marfone, P.A., Refiners Have a New Learning Curve with Shale Oil, Hydrocarbon Processing, March Kremer, L., Shale Oil Issues and Solutions, AFPM Principles and Practices Session, Salt Lake City, Utah, October Haynes, D., Tight Oil Impact on Desalter Operations, Crude Oil Quality Association Meeting, New Orleans, Louisiana, November Ohmes, R., Routt, M., Characterizing and Tracking Contaminants in Opportunity Crudes, 2013 AFPM Annual Meeting, San Antonio, Texas. 9. D. Hill, North Dakota Refining Capacity Study Final Technical Report, DOE Award No.: DE-FE , January 5, Platts Methodology and Specifications Guide, The Eagle Ford Marker: Rationale and Methodology, October Effects Of Possible Changes In Crude Oil Slate On The U.S. Refining Sector s CO 2 Emissions, prepared for the International Council On Clean Transportation by MathPro Inc., March 29, Haas, A., McElhiney, G., Ginzel, W., Buchsbaum, A., Gasoline Quality- The Measurement of Compositions and Calculation of Octanes, Petrochem./Hydrocarbon Technol. 1990, 43, Cotterman, R. L., Plumlee, K. W., Effects of Gasoline Composition on Octane Number, ACS Meeting; Miami Beach, Florida, Savage, G., Crude Preheat Management for Challenged and Unconventional Crudes, Crude Oil Quality Association Meeting, San Antonio, Texas, March Grace Catalysts Technologies Catalagram 21

24 15. Holubnyak, et. al., Understanding the Souring at Bakken Oil Reservoirs, SPE International Symposium on Oilfield Chemistry, The Woodlands, Texas, April Yaluris, G., Cheng, W.-C., Boock, L.T., Peters, M., Hunt, L.J., The Effects of Fe Poisoning on FCC Catalysts, AM NPRA Meeting, New Orleans, Louisiana. 16. Cioppa, M.T., Spatial Variations in Magnetic Components of the Devonian Birdbear Formation, Williston Basin, presented at the Geofluids VII Conference, Rueil-Malmaison, France, June Keyser, J.C., Versatile Fluidized Bed Reactor, US Patent 6,069,012, assigned to Kayser Technology, Bryden, K.J., Habib, E.T., Topete, O.A., Processing Shale Oils in FCC: Challenges and Opportunities, Hydrocarbon Processing, September Cher, Y.-Y., Koebel, J., Schiller, R., Enhanced Bottoms Cracking and Process Flexibility with Midas FCC Catalyst, Catalagram 112, W.R. Grace & Co., Fitzharris, W.D., Ringle, S.J., Nicholes, K.S., Catalytic Cracking of Whole Crude Oil, U.S. Patent 4,859,310 (1989), assigned to Amoco Corporation. 19. Masologites, G.P., Beckberger, L.H., Low-sulfur Syn Crude via FCC, Oil and Gas Journal, 71 (1973), pp Bryden, K., Weatherbee, G., Habib, E.T., Flexible Pilot Plant Technology for Evaluation of Unconventional Feedstocks and Processes AM-13-04, 2013 AFPM Annual Meeting, San Antonio, Texas. 21. Chapter 6, FCC Operation, in The Grace Davison Guide to Fluid Catalytic Cracking, Ritter, R.E., Light Cycle Oil from the FCC Unit AM-88-57, 1988 NPRA Annual Meeting, San Antonio, Texas. 23. Cheng, W.-C., Habib, E.T., Rajagopalan, K., Roberie, T.G., Wormsbecher, R.F., Ziebarth, M.S., Fluid Catalytic Cracking, in Handbook of Heterogeneous Catalysis, 2nd. Ed., 2008, pp Answers to Question 113, 2006 NPRA Q&A and Technology Forum, October 8-11, 2006, Phoenix, AZ. 29. Answers to Question 42, 2009 NPRA Q&A and Technology Forum, October 11-14, 2009, Fort Worth, TX. 30. Buchanan, J.S., Santiesteban, J.G., Haag, W.O., Mechanistic Considerations in Acid-Catalyzed Cracking of Olefins, Journal of Catalysis, Volume 158, January 1996, Pages Knocking characteristics of pure hydrocarbons, Developed Under American Petroleum Institute Research Project 45, Special Technical Publication No. 225; American Society for Testing and Materials: West Conshohocken, PA, Schipper, P. H., Dwyer, F.G., Sparrell, P.T., Mizrahi, S., Herbst, J.A., Zeolite ZSM-5 in Fluid Catalytic Cracking: Performance, Benefits, and Applications. In Fluid Catalytic Cracking, edited by Mario L. Occelli, 375: Washington, DC: American Chemical Society, Yaluris, G., The Effects of Fe Poisoning on FCC Catalysts: An Update, Catalagram 91, W.R. Grace & Co., Issue No. 114 / 2014

25 Tight Oil Distillate in ULSD Production, What To Expect? Greg Rosinski Hydrotreating Technical Service Engineer Brian Watkins Manager, Hydrotreating Pilot Plant and Technical Service Engineer Charles Olsen Director, Distillate R&D and Technical Service Advanced Refining Technologies Chicago, IL, USA Global growth in distillate demand has driven refiners to maximize their middle distillate yield while trying to manage final product properties such as cold flow properties, color, and cetane. This has been coupled with the availability of new domestic and unconventional crude oil sources and the global disparity in hydrogen cost and availability. This has given some refiners a unique opportunity to exploit different catalytic routes to maximizing middle distillate production. Catalytic solutions to increase middle distillate yield while controlling final product properties include hydrotreating, hydrocracking, and hydrodewaxing. Each of these routes present challenges in terms of hydrogen consumption, yield shifts, changes in cycle life, and the chemistry involved. In addition to new sources of crude, the price of natural gas in the North America has decreased and is significantly lower than the rest of the world (Figure 1). This has given North American refiners an incentive to pursue volume gain due to the reduced cost of hydrogen derived from natural gas. Furthermore, worldwide demand for distillates has grown, and the U.S., while still a net importer of crude oil, has become a net exporter of refined products due in part to a competitive cost advantage in hydrogen (Figure 2). ULSD comprises the largest amount of net exports, with most of the balance being gasoline and jet fuel. Thus, U.S. Refiners have been utilizing their competitive advantage in fuels production as the relative price of natural gas has fallen. In the last decade new sources of crude have also come on the market (Figure 3). Most of the increase has come from bitumen derived synthetic crudes from Canada or more recently from shale oil formations, principally Bakken and Eagle Ford. Since 2007 almost one million barrels of new synthetic crude from Canada has become available and shale formations have provided over two million barrels of additional crude to the North American market. Almost all of the new crude to come to market is captive to North America. Refiners have eagerly tried to utilize these new sources of crude due to pricing and availability, which has lead to enhanced profitability for refiners who have access to these new crude sources. Grace Catalysts Technologies Catalagram 23

26 USB/MMBTU /1/2004 7/1/2004 1/1/2005 7/1/2005 1/1/2006 7/1/2006 1/1/2007 7/1/2007 1/1/2008 7/1/2008 1/1/2009 7/1/2009 1/1/2010 7/1/2010 1/1/2011 7/1/2011 1/1/2012 7/1/2012 1/1/2013 Germany, NG Japan, LNG United States, NG FIGURE 1: World Natural Spot Natural Gas Prices Jan-04 Jul-04 Jan-05 Jul-05 Jan-06 Jul-06 Jan-07 Jul-07 Jan-08 Jul-08 Net Crude Oil Imports Jan-09 Jul-09 Jan-10 Jul-10 Jan-11 Jul-11 Jan-12 Jul-12 Jan-13 Jul-13 7/1/2013 Net Refined Product Imports FIGURE 2: Net US Imports of Crude Oil and Refined Petroleum Products Mbbls/Day 1,600 1,400 1,200 1, May-05 Bakken Eagle Ford Jan-14 1/1/2014 Oct-06 Feb-08 Jul-09 Nov-10 Apr-12 Aug-13 Dec-14 Lt. Synthetic Oil Sands Heavy FIGURE 3: Canadian Synthetic Crude Supply and U.S. Tight Oil Production The rapidly increasing availability of tight oils like Bakken and Eagle Ford have given rise to questions about the impact these crudes may have on processing units in the refinery. The questions include concerns regarding the cold flow properties, ease of processing and hydrogen consumption implications. With these questions in mind, Advanced Refining Technologies completed a study which investigated the effects of tight oil compared to a conventional crude diesel cut. The study also included LCO blends, to gain an understanding of the differences this would have on distillate hydrotreater performance. Table I summarizes the properties of the various feeds used in the study. Notice that the cloud point of the Bakken feed is not very different from other light sweet crude blends in the mid-continent region of the U.S. Also, note that the aromatics content is similar to other straight run (SR) material with similar gravity. This would indicate that the heat release should be similar to other light sweet crudes such as WTI or Brent (Table II). The sulfur content of the Bakken feed is low, and the fraction of hard sulfur is higher than expected. Furthermore, the cetane index is similar to the reference SR which is expected from similarities in API gravity and aromatics content. The analytical testing showed trace amounts of silicon in the Bakken diesel; all other contaminants were below the detection limit. ART used its newest high activity nickel molybdenum (NiMo) catalyst, 545DX for this study. 545DX is made using a new proprietary alumina technology which enhances the activity derived from ART s DX metals technology platform. This has resulted in a substantial increase in HDS, HDN, and aromatic saturation, over the previous generation of NiMo catalysts. NiMo was chosen for this study as many refiners have shown a preference for volume swell over the concern of increased hydrogen cost. The test was conducted at 1050 psi hydrogen partial pressure and 1.1 LHSV with 2800 scfb H 2 /Oil. The LCO used in both blends was from the same source. The Bakken diesel cut was from a refiner who was processing a high percentage of Bakken crude in the refinery. The straight run (SR) and LCO both came from a midcontinent refiner processing crudes from Canada. Figure 4 shows the HDS activity for each feed. At these conditions, both the SR and Bakken SR met the 10 ppm product sulfur specification at relatively low temperatures. Notice that the SR is significantly more difficult to treat requiring F higher WABT compared to the Bakken diesel. Interestingly, the addition of LCO to the Bakken SR had a much greater impact on HDS catalyst performance than the LCO addition to the reference SR. The difference in required temperature narrows substantially to only about F with the addition of 30%LCO. The reference SR/LCO blend required about 30 F higher temperature to achieve 10 ppm sulfur compared to the SR alone, while the Bakken/LCO blend required about 50 F higher temperature compared to the Bakken SR. As typical for many ultra low sulfur diesel (ULSD) 24 Issue No. 114 / 2014

27 SR SR + 30% LCO Bakken Bakken + 30% LCO Gravity, API Sulfur, wt.% Nitrogen, wppm Total Aromatics, vol.% PNA (2 + ring), vol.% Cloud Point, F Cetane Index (D976) ASTM Color L1 L5 L5 L3 Distillation (ASTM D86) IBP, F , F , F , F , F , F FBP, F Sulfur Speculation Gasoline Range Sulfur, wppm Benzothiophene, wppm C 1 -Benzothiophene, wppm C 2 -Benzothiophene, wppm C 3 -Benzothiophene, wppm C 4 +Benzothiophene, wppm Dibenzothiophene, wppm C 1 -Dibenzothiophene, wppm C 2 -Dibenzothiophene, wppm ,6-Dibenzothiophene, wppm C 3 +Dibenzothiophene, wppm % Hard Sulfur TABLE I: Feedstock Properties Product Sulfur, wppm Bakken Brent Cut Range See Table API Sulfur, wt.% TABLE II: Properties of Brent and Bakken Diesel Increase in WABT, F SR SR + LCO Bakken Bakken + LCO FIGURE 4: Comparison of HDS Activity Grace Catalysts Technologies Catalagram 25

28 units, the product nitrogen was low. Even at modest temperatures, all the feeds were below 10 wppm nitrogen, and once the 10 wppm sulfur specification was met, all were <0.5 wppm nitrogen. Figure 5 compares the total aromatic saturation of the Bakken feeds. The temperature for maximum aromatic saturation of the straight run Bakken is slightly lower compared to the Bakken/LCO blend, and the conversion is significantly higher. As shown in Table I, the nitrogen content of the LCO blend is nearly three times higher than the SR Bakken which inhibits aromatic saturation reactions. Also, the LCO blend has a higher aromatics content, which reduces the outlet H 2 partial pressure due to the higher hydrogen consumption, which affects equilibrium and limits conversion. The overall effect is the maximum saturation conversion occurs at F lower temperature and is almost twice as high with the SR Bakken. Figure 6 compares the aromatics saturation on all the feed blends. The reference SR and Bakken SR both exhibit similar aromatics saturation curves as temperature is increased. The Bakken SR appears to have higher conversion in the kinetically controlled regime, probably due to the lower nitrogen and sulfur content n the feed. The SR/LCO blend behaves similar to the Bakken/LCO blend in terms of aromatic saturation although there are some differences at higher temperature perhaps indicative of different aromatic species. Figure 7 compares the PNA saturation in the Bakken feeds. The PNA conversion on the SR Bakken is nearly 100% until thermodynamic equilibrium is reached and limits conversion. The PNA conversion on the Bakken/LCO is always lower and reaches a maximum of about 94%. Once the aromatic conversion thermodynamic equilibrium is reached, there is a fairly rapid drop off in conversion as temperature is increased. This is what is expected near the end of run in a commercial ULSD unit, and often leads to product color problems. Total Aromatic Conversion, vol.% 70.0% 60.0% 50.0% 40.0% 30.0% 20.0% 10.0% 0.0% -10.0% -20.0% Increase in Temperature, F Bakken Bakken + LCO FIGURE 5: Total Aromatics Saturation on Bakken Diesel Total Aromatic Conversion, vol.% 70.0% 60.0% 50.0% 40.0% 30.0% 20.0% 10.0% 0.0% -10.0% -20.0% Increase in Temperature, F SR SR + LCO Bakken Bakken + LCO FIGURE 6: Total Aromatic Saturation for All Feeds Figure 8 compares the PNA conversion on all the feeds tested. It is interesting to note that the PNA conversion when processing the Bakken feeds decreases more rapidly and approaches equilibrium sooner than the other feeds. This is likely due to a difference in the PNA distribution in the Bakken crude. It is generally accepted that PNA conversion has an influence on product color, and in particular, three ring aromatics have been shown to significantly impact product color 1. Since the PNA conversion decreases faster with increasing temperature when processing the Bakken blends, the product color achieved from each of the blends was also investigated. Figure 9 summarizes the product color for each of the feeds that were tested. As observed with the PNA conversion, both the Bakken straight run and the reference SR show a similar change in product color with increasing reactor temperature. However, the Bakken SR product PNA Conversion, vol.% 110% 100% 90% 80% 70% 60% 50% Increase in Temperature, F Bakken Bakken + LCO FIGURE 7: PNA Conversion on Bakken Diesel 26 Issue No. 114 / 2014

29 PNA Conversion, vol.% 110% 100% 90% 80% 70% 60% 50% Increase in Temperature, F SR SR + LCO Bakken Bakken + LCO FIGURE 8: PNA Conversion on all Four Feed Blends ASTM Product Color Increase in Temperature, F SR SR + LCO Bakken Bakken + LCO FIGURE 9: Comparison of Product Color Processing Various Feed Blends API Gain Increase in WABT, F SR SR + LCO Bakken Bakken + LCO 160 color begins to increase at a lower temperature compared to the reference SR. This is consistent with the PNA conversion shown in Figure 8. Adding LCO to the SR feeds results in higher product colors even for lower temperatures. The temperature at which the product color begins to degrade further is also lower for the LCO blends consistent with the behavior described for PNA conversion. Figures 10 and 11 show the API gain and the cetane lift respectively. As might be expected, the Bakken SR shows the lowest API and cetane lift, which is due in part to the lower sulfur level which is about 10% of that in the reference SR. Even though the total aromatic content of the Bakken feedstock is similar to that of the reference SR feed, the lower feed sulfur is a driving force for lower API upgrade and volume swell. Interestingly, the API increase and cetane lift of the reference SR and the Bakken/LCO blend are almost the same. This is due in part to a greater shift in distillation shift caused by the LCO, as cetane is a function of both API and distillation. The LCO blend also has much higher PNA content which plays a role in API and cetane improvement as well. For the most part, hydrotreating does not change the cloud point substantially. This testing confirms that over the typical operating range, the cloud point stays within a fairly narrow window of +/- 5 F of the feed. Both LCO blends have products with cloud points a few degrees above the feed. The LCO blends must contain naphthenic type species that have a higher cloud point than the feed. All the feed blends show a decrease in cloud point as the temperature increases substantially from start of run. This may be indicative of some cracking that occurs at high temperatures converting molecules with higher cloud points to molecules with lower cloud points. This data does show that the cold flow properties of Bakken are not significantly different than the other feeds in this study. With the concern over the cold flow properties of tight oils it is worthwhile to examine how they compare to other crudes, including some synthetic crudes (Table III). Looking at the assays of several well known crudes, the cloud points of the diesel fractions vary between F depending on the source, and the Bakken appears to be no different. The interesting thing to note is the low cloud points of the Canadian synthetic crudes. Canadian synthetic crudes are typically produced with some form of hydroprocessing and or coking so they have higher amounts of naphthenes; thus, these crudes have lower cloud points, compared to conventional crudes. If it made sense for the refiner and they were cloud point constrained, then switching to some synthetic crude may be a sound choice, as opposed to using a dewaxing catalyst which will increase naphtha yield at the expense of distillate yield 3. This would have to be balanced against the economics of the refinery as a whole. FIGURE 10: Difference in API Increase Grace Catalysts Technologies Catalagram 27

30 Crude Cutpoints ( F) Cloudpoint ( F) Conventional Bonny Light Brent Dubai Forties Ural Southern Green Canyon Blend Maya Canadian Synthetic Cold Lake Kearl Western Canadian Select Blend Synbit SHB (Surmont Heavy Blend) TABLE III: Cloud Point of the Diesel Fractions of Various Crudes SR SR/LCO Bakken Bakken/LCO WABT Base +33 F -41 F +10 F API Change Sulfur, wppm Nitrogen, wppm Total Aromatics, vol.% PNA, vol.% Cetane Lift Delta Cloud H 2 Consumption, SCFB TABLE IV: Comparison of Product Properties at 10 wppm Sulfur Table IV compares the product properties from all the feeds at a product sulfur of 10 wppm. As expected, the Bakken diesel has a very low temperature for 10 wppm product sulfur. This is primarly due to the low feed sulfur, which is approximately 0.1 wt.%, whereas the other feeds have sulfur levels closer to 1 wt.% or greater. The cetane lift and API gain of the Bakken are also noticeably lower compared to the other feeds. All of these indicate lower hydrogen consumption for the Bakken SR compared to the other feeds. A breakdown of the hydrogen consumption at constant product sulfur by compound type is shown in Figure 13. The lower required temperatures shown in Table III result in much lower total aromatic and PNA saturation for the Bakken SR feed. This, combined with the very low sulfur conversion required to achieve 10 ppm product sulfur, contributes to the lower overall hydrogen consumption. It is expected that most refiners will be blending in LCO and/or light coker gas oil which will increase the hydrogen consumption over the Bakken SR feed. The Bakken/LCO blend appears to behave API Gain Increase in WABT, F SR SR + LCO Bakken Bakken + LCO FIGURE 11: PNA Comparison of Cetane Uplift Issue No. 114 / 2014

31 Cloud Point Change (Product - Feed), F Increase in WABT, F SR SR + LCO Bakken Bakken + LCO FIGURE 12: Change in Cloud Point of the Various Feed Blends Estimated Hydrogen Consumption, SCFB SR Sulfur SR/LCO Bakken Bakken/LCO Nitrogen Total Aromatics PNA FIGURE 13: Comparison of Hydrogen Consumption at 10 ppm Sulfur 160 much like the reference SR feed in terms of SOR temperature and hydrogen consumption. The lower hydrogen consumption with the Bakken SR feed may cause a heat balance issue if the unit was originally designed for processing feed from a heavier crude slate, and the Bakken displaced some of the heavy crude. Figure 14 compares the heat release for the different feeds. Consistent with the hydrogen consumption just discussed, the heat release from the Bakken is significantly lower than that for the other feeds, and the Bakken/LCO looks similar to the reference SR feed. As with any crude change, Bakken can present some challenges depending on the refinery configuration. However, diesel derived from Bakken crude appears from this analysis, to be similar to other light sweet crudes in terms of feed characteristics and its behavior during hydrotreating. If the refiner is prepared for crudes similar to Bakken, then there should be minimal problems in processing Bakken crude. There may be opportunities for catalyst selection to help maximize performance when processing this or other opportunity crudes. Advanced Refining Technologies LLC has the ability to conduct detailed customer-specific pilot plant testing to provide the refiner the confidence and understanding of the various options available when considering a catalyst change. Both the hydrotreating catalyst system and the operating strategy for the ULSD unit are critical for providing the highest quality products. Use of tailored catalyst systems can optimize the ULSD hydrotreater in order to produce higher quality products while utilizing the greatest flexibility of feedstocks. The complex relationship between hydrotreater operation and catalyst kinetics underscores the importance of working with a catalyst technology supplier that can tailor product offerings for each refiner s unique operating conditions. This knowledge enables ART to meet the refiner s objectives and maximize revenue. Estimated Heat Release, BTU/bbl References 1. Rosinski, G., C. Olsen and B. Watkins, Factors Influencing ULSD Product Color, Advanced Refining Technologies ; Catalagram 105, Watkins, B., Olsen, C., Custom Catalyst Systems for Higher Yields of Diesel AFPM Annual Meeting, Paper AM Watkins, B., Lansdown, M., Understanding Cloud Point and Hydrotreating Relationships Catalagram 112, SR Sulfur SR/LCO Bakken Bakken/LCO Nitrogen Total Aromatics PNA FIGURE 14: Heat Release at 10 ppm Sulfur Grace Catalysts Technologies Catalagram 29

32 Two Companies Joined to Develop a Catalytic Solution for Bottoms Upgrading to Diesel in the FCC Unit William Morales Hipolito Rodriguez Luis Javier Hoyos Tania Chanaga Luis Almanza Ecopetrol-Instituto Colombiano del Petróleo (ICP) Colombia Uriel Navarro Larry Hunt Clemencia Marin Hongbo Ma Rick Wormsbecher Tom Habib Grace Catalysts Technologies Columbia, MD, USA Summary The objectives for this project were developed after an in-depth analysis of the local and world situation of the refining opportunities for diesel production, and of the existing catalyst technologies in the market. The project s team considered the following objectives: 1. Develop an FCC catalyst to increase the LCO (light cycle oil) yield by 3 vol.% 2. Increase the Cetane Index (CI) of the LCO by 4 numbers 3. Maximum gasoline loss of 2 vol.%, while maintaining the Octane number. All of these results were required at constant coke when compared to a base catalyst of adequate zeolite and matrix surface areas. The catalyst results in one of the commercial FCC units of Ecopetrol in the Barrancabermeja refinery were: Increase of 2.3 vol.% in the LCO yield Increase of 3 numbers in the CI Decrease of 1.5 vol.% in gasoline yield, while maintaining octane number. Introduction The largest company in Colombia, Ecopetrol, and the world leader of FCC catalysts, Grace, joined their efforts, talents and resources in a technology innovation project to mitigate the deficit of diesel fuel in Colombia. Local and global market trends showed that the growth in the demand for diesel is greater than for gasoline. Several factors were key in developing the project s objective to maximize LCO production, such as: 1. The conversion capacity of Ecopetro s refineries, based upon FCC technology; 2. An increase in crude oil slates that are steadily richer in heavy oils; 3. The absence of specific catalyst solutions to meet the diesel objectives; 4. LCO is an important component in the streams being sent to diesel hydrotreating units. 30 Issue No. 114 / 2014

33 This article presents the following stages of this joint development project: 1. The experimental design to obtain the best formulations for the catalysts 2. Laboratory testing 3. Development of the deactivation and simulation procedures for equilibrium catalyst (Ecat) 4. Evaluation in the DCR Circulating Riser pilot plant and the scale-up using a simulation model 5. Commercial evaluation in an FCC unit at Ecopetrol s refinery in Barrancabermeja. In the catalysts design phase, the following factors were considered: the impact of the type and quantity of the zeolite and matrix; the concentration of Rare Earths (RE 2 O 3 ); as well as the catalyst stability and selectivity in a high contaminant metals environment (>10,000 ppm of Ni+V). The best formulations evaluated in the ACE reactors showed increases of 4.0 wt.% in LCO yield and nearly 4 numbers of CI. The evaluation of catalysts in the DCR pilot plant showed an incremental LCO yield of 3.0 wt.% with an improvement in CI of 3 numbers. Recognizing that in resid cracking the coke selectivity of the catalyst is one of the most important properties, great efforts were made for its optimization. The industrial plant scale-up allowed us to corroborate the excellent coke selectivity of the developed catalyst, and the simulations performed confirmed the incremental LCO yields and quality derived from the best formulation. The most important stage of a catalyst development project is its evaluation in the real world of a commercial plant. A commercial trial was started in April 2013 maintaining an average of 25% of resid in the feed throughout the test. The main goal for both companies was to corroborate the lab and pilot plant results in Ecopetrol s commercial unit, as well as to reach the objectives programmed for the project. These were confirmed. Improved coke selectivity was also evident in the commercial FCC unit, which provided a better heat balance and increased operational flexibility. Experimental Design The first step of this project was to identify the catalyst s parameters that affect LCO selectivity (distillation range C [ F]) while minimizing any gasoline yield loss. These were: 1. High surface area matrix with good bottoms cracking selectivity Moderate activity to improve LCO conversion while avoiding excessive LCO cracking. 3. Good coke and gas selectivity in resid cracking (fraction 550 C+[1022 F+]). Figure 1 shows a diagram of the experimental design for this project. To select the matrix, 8 different commercial catalysts were evaluated in a fluidized bed micro-reactor (ACE) unit 2. The ACE unit was run at the following conditions: RxT: 505 C [941 F]; C/O ratios of 4, 6 and 8; reaction time 30 sec. The variables that will be optimized are: zeolite content, RE 2 O 3 concentration in the catalyst, and matrix level. Twenty different catalyst formulations were prepared. To deactivate fresh catalysts and simulate the Ecat, two methods were used; Grace CPS-1 3 method and a method developed for this project by ICP (called IDM) 4,5. To develop this IDM method, an Ecat sample that contained the selected matrix was taken from a commercial unit. Then, in the lab, the effect of operating variables such as residence time, deactivation temperature and steam flow were determined, until the optimal conditions were defined that would simulate the physical-chemical properties, the activity and the selectivity of this Ecat. After the catalyst deactivation by the IDM method at 12,000 ppm of Ni+V equivalent, the pilot plant (DCR) studies were run. These studies were performed at the Colombian Petroleum Institute (ICP) [Instituto Colombiano de Petróleo] in isothermal conditions 5, at RxT of 525 C [977 F] and C/O ratio between 4 and 17. For coke optimization it was necessary to optimize the proportion and the type of V and Ni traps. With the results obtained from the DCR unit, a scale-up was performed to a commercial unit, using a commercial model for simulation and optimization. Finally, the commercial trial was performed in an FCC Orthoflow Unit at the 1 1 Matrix Selection 2 Variable Optimizations in ACE Unit 3 Ecat Simulation 4 DCR Study Optimum Formulations 5 Coke Optimization 6 Pilot Plant Scale-up 7 Commercial Trial FIGURE 1: Experimental Methodology Grace Catalysts Technologies Catalagram 31

34 34 32 LCO, wt.% LCO Yields, wt.% Conversion, wt.% 29.5 Rare Earths Zeolite Content FIGURE 2: LCO Selectivity Defines Test Matrix FIGURE 3: Optimization of Catalyst Formulation Ecopetrol refinery in Barrancabermeja. The feed used by the laboratory for the entire project is a blend of 70 vol.% VGO (vacuum gasoil) and 30 vol.% DMO (demetalized oil, obtained in the DEMEX unit of the Barrancabermeja refinery). This blend has the following properties: 18.5 API Gravity, 2.5 wt.% sulphur, 2.3 wt.% CCR (Conradson Carbon Residue) and 10 ppm of Ni+V. Results and Discussion Shown in Figure 2 are the results of the ACE tests (LCO yield as a function of the conversion) to select the catalyst s matrix. These eight (8) catalysts were previously deactivated by the CPS-1 method. This chart shows that catalyst 2 presents higher LCO performance within a reasonable operational range for an FCC unit. In addition, it showed the best bottoms conversion and a good coke selectivity in metals-free testing. Based on these results, this matrix platform was selected as the most appropriate to meet the project objectives, and then the other catalyst variables were optimized. Shown in Figure 3 is the experimental design of this phase of the project, where the aforementioned variables were evaluated in the following ranges: zeolite content (5-30 wt.%), RE 2 O 3 concentration (0-6 wt.%) and the matrix level (20-40 wt.%). In this three-dimensional chart we observe that the maximum LCO performance is in the range of wt.% matrix. Based on the different formulations that were studied, the best catalysts were selected for later studies. The two best formulations, among the 20 prepared, were used to study coke selectivity in a high metals environment, where it was necessary to optimize the V and Ni traps. We also needed to investigate the effect of the deactivation mode on the coke selectivity of the FCC catalysts in order to handle resid feedstocks. We did this because it was observed that the deactivation methods used had been developed for catalyst technologies designed for gasoline mode operations. Therefore, ICP developed the IDM deactivation method to simulate the properties of this type of catalyst technology to maximize LCO. Table I shows the activity and coke selectivity results for the two best catalysts comparing the two different deactivation procedures, ICP (IDM method) and Grace (CPS method) at constant conversion (50 wt.%). These results allow us to conclude that the IDM method, at similar metals levels (Ni+V), completely changed the relative activity and coke selectivity of the two deactivated catalysts. The catalyst deactivated by the IDM method required lower C/O ratio to reach the same conversion level with lower coke production. That is, after the hydrothermal deactivation, these catalysts were more active with better coke selectivity, since the IDM method produced a better matrix deactivation (higher Z/M ratio), hence minimizing the catalytic coke produced in the matrix structure. The higher activity (lower C/O) is related to the higher zeolite surface area. The better coke selectivity is related to the lower matrix area and the higher zeolite area, which means higher zeolite/matrix ratio, as is shown in Table I. This important result shows once more that all investigations can benefit from developing its own methods and analytical techniques that allow for correctly evaluating and studying new catalyst technologies. In this case, it can be concluded that the IDM method better simulated the catalyst technologies containing high levels of an active matrix that is designed to increase bottoms conversion to LCO. The results obtained in the DCR pilot plant were used to perform the scale-up to the commercial plant using a proprietary model of ICP, which is tuned with the commercial plant data. This scale-up allows us, through information from the pilot plant, to calculate kinetic parameters that are associated with the catalyst of origin. Once obtained, these parameters are fed to the simulator to proceed under optimization mode to find the optimal operational conditions for the commercial unit. The FCC process model from 32 Issue No. 114 / 2014

35 Cat 1 Grace CPS NCat 1 ICP IDM Cat 2 Grace CPS Cat 2 ICP IDM Conversion, wt.% C/O Ratio Coke, wt.% Zeolite/Matrix Ratio Ni, ppm V, ppm TABLE I: Effect of the Catalyst Deactivation Procedure on the Catalyst Properties Operating Conditions Original Base Case New Base Case ICP-4C Total Feed Rate, BPD Recycle of HCO, BPD Reaction Temperature, C Feed Preheat Temperature, C Cat/Oil Ratio Regenerator Temperature, C Product Yields Conversion, vol.% Dry Gas (H 2, C 1, C 2, C 2 =, H 2 S), vol.% LPG (C 3, C 3 =, C 4, C 4 =), vol.% Gasoline (C C), vol.% LCO, ( C), vol.% HCO, ( C), vol.% Bottoms, 427+ C, vol.% Coke, wt.% LCO Cetane Index TABLE II: Operating Conditions and Yields for the DCR Pilot Plant Scale-up the scale-up of pilot plant data allows us to perform the heat balance of the commercial unit for each evaluated catalyst. Additionally we are able to perform optimizations toward specific products based upon the needs of the refinery, taking into consideration the operational restrictions of the unit. Table II shows the scaled-up results. There are two base cases shown, reflecting that during the project timeline, the base catalyst was changed as well as the FCC unit where the commercial trial was performed. The original base case was used to define the project s objectives, while the second base case was established from the FCC unit where the newly developed catalyst was tested. In these simulations there is a recycle effect, since it was considered that recycling heavy cycle oil (HCO) was a good practice for maximizing LCO production. The operating conditions allow us to conclude that the developed catalyst (ICP-4C) is more coke selective, since it produces a drop between 7-8 C [ F] in the regenerator temperature at constant operating conditions. The yields reported with ICP-4C allow us to conclude that there is an increase of 4.3 vol.% in LCO yield compared to the first base case, and of 2.3 vol.% compared to the second base case, with an increase in the cetane index of 2.8 numbers. On the other hand, the decrease in gasoline yield was 1.1 vol.%. These results allowed us to meet the project s objectives and to start preparations for the commercial trial. The commercial trial in one of the FCC units of Barrancabermeja refinery started on April 23, In Table III, we present the main results from that trial, where the new catalyst (ICP-4C) had an 80% turnover in the Ecat inventory. The feed during the trial was 77 vol.% of VGO and 23 vol.% of DMO, which was 8% more resid (DMO) than the respective base case; so it was a slightly heavier, more refractory feedstock. The obtained yields, compared to the second base case, allowed us to corroborate that the developed catalyst maintained the main operating conditions while processing a slightly heavier feedstock. It was observed that ICP-4C provided Grace Catalysts Technologies Catalagram 33

36 Base Case Evaluation 80% Turnover Composition (VGO-DMO), vol.% Metals Content (Ni+V), ppm Basic Nitrogen, ppm Conradson Carbon Residue, wt.% Sulphur Content, wt.% API Gravity, ÅPI Ecat Ni+V, ppm Operating Conditions Total Feed Rate Reaction Temperature Feed Preheat Temperature Dense Phase Regenerator Temperature Dilute Phase Regenerator Temperature Cat/Oil Ratio Fresh Catalyst Addition Rate Product Yields Dry Gas (H 2, H 2 S, C 1, C 2, C 2 =), wt.% Total LPG (C 3, C 3 =, C 4, C 4 =), vol.% Naphtha (C C), vol.% LCO, ( C), vol.% HCO, ( C), vol.% Slurry (399 C), vol.% Coke, wt.% Conversion, vol.% LCO Cetane Index Net Economical Benefits, USD/bbl TABLE III: Yields and Operating Conditions of the Commercial Trial a significant decrease in the dry gas production. LCO production was increased by 2.3 vol.% while the cetane index increased by 3 numbers. The decrease in gasoline yield was only 1.5 wt.%. According to the economic evaluation, the ICP-4C catalyst operation achieved an economic benefit for the refinery of 0.34 USD/bbl. The most important conclusion of this project was that the successful strategic alliance of Ecopetrol and Grace to develop a catalyst provided valuable benefits for both companies, while achieving the objectives initially set for the project. 3. D. Wallenstein, R.H. Harding, J.R.D. Nee, and L.T. Boock, Recent advances in the deactivation of FCC catalysts by cyclic propylene steaming (CPS) in the presence and absence of contaminant metals. Appl. Catal. A: General 204 (2000): Grace Davison, Guide to Fluid Catalytic Cracking, Part three, Chapter Luis O. Almanza, Simulation of FCC equilibrium catalyst age distribution by using a deactivation model, Studies in Surface Science and Catalysis. Vol. 166, Edited by Dr. M. L. Occelli. References 1. Larry Hunt, Maximize bottoms upgrading with MIDAS, Davison Catalagram 98, J. C. Kayser, US Patent Versatile fluidized bed reactor, assigned to Kayser Technology, Luis O. Almanza, Irreversible deactivation model of the FCC catalyst, XII Colombian Chemical Engineering Congress, Manizales, August Grace Davison, Guide to Fluid Catalytic Cracking, Part one, Chapter six. 34 Issue No. 114 / 2014

37 People on the Move Bob Gatte has been named Vice President and General Manager, Refining Technologies. Reporting directly to Bob will be Dennis Kowalczyk, General Manager Americas; Andre Lanning, General Manager EMEA; Jim Nee, General Manager Asia Pacific; Wu-Cheng Cheng, Director R&D. Europe and Africa will be led by Michel Melin as General Sales Manager Europe & Africa. In this new role, Gilles Bourdillon, Matthias Scherer and Ivo Peros will report directly to Michel. Michel will also keep his current role as Director Technical Service with Stephane Montmasson continuing to report to Michel as well. Simon Reitmaier joined this team as Technical Sales Manager in December Kevin Burton has been promoted to the position of National Technical Sales Leader, reporting to Dennis Kowalczyk. In this role, Kevin will serve as a commercial technical sales and service team leader in the North America Refining Technologies business. He will be the primary contact for key global refining accounts and will be responsible for strategy development and implementation within the Western region of North America. Kevin will continue to be based in California. Kathy Chrien has been named RT Global Demand Leader. Prior to her new role, Kathy held the position of S&OP Leader, Refining Technologies Jason Zhou joined Grace in January 2014 as Sales Director, China, based in Shanghai, China Gary Cheng, who joined Grace in January 2014 as FCC Technical Service Representative will report to Kevin. Ljubica Simic has joined Grace as the Technical Sales and Service Manager, Refining Technologies (RT). In this role, Ljubica is responsible for Sales and Technical Service for RT Catalysts to our current and prospect customers in Central and Eastern European countries. Refining Technologies EMEA has announced the following sales/service organization: Middle East and CIS countries will be led by Nagib Haidar as General Sales Manager ME & CIS. Vladimir Jegorov and Nathan Ergonul will continue reporting directly to Nagib in his new role. Congratulations to former Catalagram editor, Tom Habib, on his retirement from Grace with 34 years of service. Tom has served on the AFPM panel and is the author or co-author of numerous AFPM and industry technical presentations. Grace Catalysts Technologies Catalagram 35

38 Meeting Tier 3 Gasoline Sulfur Regulations Brian Watkins Manager, Hydrotreating Pilot Plant and Technical Service Engineer Advanced Refining Technologies Chicago, IL, USA John Haley Director, Marketing & Business Development Rosann Schiller Marketing Director, FCC Commercial Strategy Grace Catalysts Technologies Columbia, MD, USA Almost one year after first proposing the stricter vehicle emissions standards known as Tier 3, the US Environmental Protection Agency (EPA) finalized the new regulations on March 3, Tier 3 requires the U.S. oil industry to reduce the average sulfur level in gasoline by more than 60 percent, to just 10 parts per million (ppm) in 2017, from the current 30 ppm. Unlike regulations in parts of Europe and Japan, the U.S. regulations allow for refinery gate sulfur levels as high as 80 ppm so long as the volume weighted average is maintained at or below 10 ppm. Based on Tier 2 compliance experience, the EPA projects that an average standard gasoline target, combined with a higher cap will allow refiners batch-to-batch flexibility while reducing the overall sulfur level. The EPA also believes that this system will allow refiners to minimize operating costs. Tier 2 experience supports these assumptions. In 2012, under Tier 2, the national gasoline average pool sulfur was 26.7 ppm, 3.3 ppm below the target of 30 ppm. Tier 3 continues the Tier 2 credit trading plan, where credits are generated for gasoline produced below the average target gasoline sulfur. Also, credits accumulated under Tier 2, which have a five year life, can be carried over for Tier 3 compliance. At current gasoline sulfur levels, if refiners continue to accrue credits at the current rate until 2017, Tier 3 implementation could potentially be delayed 1 year. By averaging 20 ppm for 2.5 years leading up to 2017, refiners could delay implementation of Tier 3 standards until mid Adding the 3.3 ppm of credits accumulated in 2012, 2013, and the first quarter of 2014, refineries could possibly delay investments in capital to meet Tier 3 compliance until Also, small volume refineries, representing approximately 1/3 of U.S. refineries, are exempted from compliance until Credit trading is described by the EPA as robust and fluid. According to EPA data, 56% of 2012 credits were transferred intercompany and 44% of 2012 credits were traded intracompany, that is, traded outside the company where they were generated. Credits allow refiners to delay capital spending, and in some cases may allow refiners to minimize capital spending. To meet Tier 3 targets, the EPA predicts that average FCC gasoline sulfur will have to be equal to or lower than 25 ppm, compared to the current average FCC gasoline sulfur of 80 ppm, assuming that FCC gasoline represents 36% of the total gasoline pool. Much of the Tier 3 gasoline sulfur compliance focus is on FCC gasoline. With the exception of the combined Light Straight Run (LSR) and Natural Gas Liquids (NGL) stream, which currently represents 5.2% of the gasoline pool with a current average sulfur level of 15 ppm, the FCC stream is the only stream that does not meet the new Tier 3, 30 ppm average sulfur target. Compliance with Tier 3 regulations will require adjustments to operating strategies and, most likely, capital investment for new or upgraded equipment. Hardware options available to reduce FCC gasoline sulfur include FCC feed pre-treatment or gasoline post-treatment. 36 Issue No. 114 / 2014

39 FCC Gasoline Sulfur, ppm 100,000 10,000 1, , ,000 FCC Feed Sulfur, ppm FIGURE 1: Relationship between FCC Gasoline Sulfur and FCC Feed Sulfur FCC Feed Pre-Treatment FCC feed hydrotreating typically lowers FCC feed sulfur by 70-90%. FCC units running hydrotreated feedstocks produce gasoline in the range of 200 to 500 ppm. If the hydrotreater is operated at high severity high temperature and pressure the resulting FCC gasoline sulfur level would typically be in the range of 75 to 100 ppm. Operating at higher severity requires more frequent catalyst change outs, increased hydrogen, and increased maintenance, and, therefore, increased operating cost. And to meet Tier 3 levels, other changes in the pre-treater operation might need to be considered. To address these needs, Advanced Refining Technologies LLC (ART) utilizes the ApART TM catalyst system for FCC pre-treatment. This technology is designed to provide significant increased HDS conversion while at the same time providing significant upgrading of FCC feedstock quality and yields. In essence, an ApART TM catalyst system is a staged bed of high activity NiMo and CoMo catalysts where the relative quantities of each catalyst are optimized to meet individual refiner s goals and constraints. ART continues to develop a better understanding of the reactions and kinetics involved in FCC pre-treating, and through its relationship with Grace, a detailed understanding of the effects of hydrotreating on downstream FCC performance. The hydrotreating catalyst system and the operating strategy for the pre-treater are critical to providing the highest quality feed for the FCC. FCC pre-treating plays an important part in reducing the sulfur content of FCC products. ART has completed many studies looking into the effects of hydrotreating on FCC performance and the quality of the FCC products. This work confirms that increased severity of the pre-treater operation results in a reduction in FCC gasoline sulfur. Figure 1 shows the relationship between FCC feed sulfur and the resulting sulfur of the FCC gasoline. This presented in Figure 1 was generated using a variety of FCC feeds that had been hydrotreated over several types of catalysts and catalyst systems. The results demonstrate good correlation between FCC feed sulfur and the corresponding FCC gasoline sulfur. However, increasing the severity of the pre-treater operation to reduce product sulfur will tend to move the catalyst towards more of a poly nuclear aromatic (PNA) mode of operation. The PNA mode of operation, while beneficial to the FCC in many ways, can shorten the cycle length of the pre-treater catalyst due to the increased temperatures. Operating the hydrotreater to remove nitrogen and PNA's improves FCC product value when targeting gasoline production, but this needs to be balanced against the increased costs of higher hydrogen consumption and shorter cycle. Tailored ApART TM catalyst systems with 586DX and AT795 optimizes the production of high quality feeds to the FCC and production of lower sulfur FCC gasoline, providing additional benefit if the FCC gasoline sulfur is low enough to be blended directly into the gasoline pool without additional post treating, or requires less severe post treating. Post-Treating FCC Gasoline Hydrotreating FCC gasoline can have a dramatic, negative effect on the gasoline octane due to the additional olefin saturation that occurs when removing the last amount of sulfur. The impact of gasoline post treatment on gasoline octane is related to the severity of the post treater operation. In the range of 96-99% sulfur removal, the impact on octane and hydrogen use is exponential. The impact on gasoline octane across all technologies, operated at moderate severity, is approximately 0.8 R+M/2. Undercutting Gasoline The EPA estimates that 22% of FCC gasoline was undercut to distillate in 2009 and expects that to increase to 68% by With much of the FCC gasoline sulfur concentrated in the high boiling point tail, undercutting can significantly lower gasoline sulfur. The EPA predicts that if the naphtha swing cut is fully cut into the distillate pool, that FCC gasoline volume could be reduced by 16%, and that FCC gasoline sulfur could be reduced by 50%. However, the EPA believes that market forces will drive undercutting gasoline to diesel, as diesel demand increases amid decreasing gasoline demand. Grace Catalysts Technologies Catalagram 37

40 Gasoline Sulfur/Feed Sulfur, % 3.0% 2.8% 2.6% 2.4% 2.2% 2.0% 1.8% 1.6% Base SuRCA 1.4% SuRCA Reduced Gasoline Sulfur 1.2% Selectivity by 40% at Constant Gasoline Cut Point 1.0% SIMDIST Gasoline T99, F FIGURE 2: SuRCA Performance at Japanese Refiner FCC Catalytic Gasoline Sulfur Reduction Refiners around the world have demonstrated that use of gasoline sulfur reduction catalysts and additives is a cost-effective component of their clean fuels strategy. The benefits of in-unit catalytic FCC gasoline sulfur reduction are specific to the refinery s configuration, yield targets, and financial goals. However, some examples can be drawn from current applications. Grace GSR technologies: D-PriSM, SuRCA, and GSR 5, are the result of almost two decades of innovation. Grace s gasoline sulfur reduction products have been used in over 100 FCC applications worldwide to provide 20%-40% sulfur reduction in FCC naphtha, including applications in Japan and Europe, where gasoline sulfur is already regulated to a 10 ppm cap. With much of Tier 3 compliance focused on the high sulfur FCC gasoline stream, in-unit reduction of FCC gasoline sulfur with Grace s patented gasoline sulfur reduction technologies creates a variety of opportunities and options for refiners to drive profitability while meeting Tier 3 gasoline requirements. Grace s clean fuels solutions create economic advantages around feedstock blending and asset optimization to: Preserve octane Maximize throughput Extend pre-treatment and/or post-treatment hydrotreater life Provide more flexible gasoline stream blending options Provide operating flexibility during hydrotreater outages Generate gasoline sulfur ABT credits to defer capital investment Commercial Application of Grace FCC Gasoline Sulfur Reduction Technologies In the mid 2000 s, Japan committed to lower gasoline sulfur. As early adopters of more stringent gasoline quality regulations, Japanese refiners faced similar challenges that US refiners face today in meeting Tier 3. Since 2005, Japanese refiners have successfully utilized Grace s gasoline sulfur reduction products to maintain compliance and meet the 10 ppmw gasoline specifications 2. Most refiners in Japan have elected to heavily hydrotreat FCC feedstocks and therefore base gasoline sulfur levels are extremely low by worldwide standards. The sulfur content of FCC gasoline blended into the gasoline pool typically must be 15 ppm or less, but varies with each refinery. Most refiners in Japan have also elected to install FCC gasoline hydrotreaters and have taken steps to modify FCC feed properties to meet the stricter gasoline sulfur limits. The sulfur content of hydrotreated FCC feed is typically in the range of 700 ppm to 3000 ppm. The severity of the hydrotreating operation needed to achieve these levels limits the life of the hydrotreating catalyst to 1-2 years. 38 Issue No. 114 / 2014

41 D-PriSM GSR 5 SuRCA Sulfur Reduction Range 20%-30% 20%-35% 20%-40% Operating Mode Full or Partial Burn Full Burn Full Burn Usage Rates (% of Inventory) 10%-15% 25% 100% TABLE I: Grace GSR Family of Products The use of SuRCA in the FCC unit reduces gasoline sulfur levels by percent. By using SuRCA, FCC feed sulfur could be increased and the refiner would achieve the same FCC gasoline product sulfur as was produced on the lower sulfur feed. Increasing FCC feed sulfur accomplished by reducing the severity of the upstream FCC feed hydrotreater will extend the life of the FCC feed hydrotreater catalyst. SuRCA catalyst technology can also be used to reduce the severity of FCC gasoline hydrotreaters. Lower sulfur in the feed to the gasoline hydrotreater allows lower severity operation to achieve a given product sulfur level. Lower severity has the benefit of reducing octane loss across the gasoline hydrotreater. Other benefits of FCC gasoline sulfur reduction technology include the potential to increase cut point (T90) of the FCC gasoline, which increases gasoline yield. Some refiners in Japan are also hydrotreating only a portion of the FCC gasoline stream and using SuRCA catalyst to optimize overall refinery production of low sulfur gasoline. Case Study: Japanese Refiner (Ongoing User) This FCC unit processes 100% hydrotreated VGO feed. The unit charge rate is 40,000 barrels per day and it is operated in full burn. Using SuRCA, the refinery realized a 40% reduction of HCCG (gasoline) sulfur at constant feed sulfur. The ratio of gasoline sulfur to feed sulfur at constant gasolinet99 is shown in Figure 2. Conclusions Grace s multiple product offerings allow for a truly custom clean fuels solution for your refinery s Tier 3 compliance plan. Grace s current range of FCC gasoline sulfur reduction products is shown in Table I. In challenging environments like Japan, where gasoline sulfur specifications are more severe than the new U.S. Tier 3 regulations, refiners use Grace products to realize 20-40% reductions in gasoline sulfur, and provide feedstock and operating flexibility. With the new Tier 3 regulations in the U.S., Grace s gasoline sulfur reduction products can also be used to generate credits to optimize investment options. Additionally, ART, Grace s JV with Chevron, provides a full slate of FCC feed pretreatment products to optimize product sulfur levels and yields. Ask your Grace representative which solution is best for your operation. References 1. Assessment and Standards Division, Office of Transportation and Air Quality, U.S. Environmental Protection Agency, Control of Air Pollution from Motor Vehicles: Tier 3 Motor Vehicle Emission and Fuel Standards Final Rule, Regulatory Impact Analysis, Washington, D.C., U.S.A., March L. Blanchard, T. Oishi, B. Teo, J. Haley, "SuRCA Catalyst Reduces Gasoline Sulfur at Three Japanese Refineries", Catalagram 98, SuRCA was applied over a base Grace catalyst. No shifts in product selectivities or gasoline octane were observed. Yields and selectivities of any SuRCA catalyst can be adjusted through reformulation of the catalyst. This refiner continues to use SuRCA today to allow them to either blend high sulfur coker gasoline into their gasoline pool or extend the catalyst life of their FCC feed VGO hydrotreater. Grace Catalysts Technologies Catalagram 39

42 Refining Technologies Team Holds Tech Seminar for Orpic Members of the Refining Technologies (RT) team welcomed 29 Oman Oil Refineries and Petroleum Industries Company (Orpic) employees to Grace's fourth Orpic RFCC Technology Seminar February 11-13, 2014 at the Crowne Plaza, Sohar Conference Centre in Oman. Orpic is a valued Grace customer and the highly interactive program was supported by Orpic senior management. The event was lead by senior members of Grace's RT EMEA team including Michel Melin, General Sales Manager and Director of Technical Service; Stefan Brandt, Director R&D; Nathan Ergonul, Technical Services and Sales Manager, Middle East; and Talal AI-Rawahi, Technical Service Manager, Middle East. Attendees were provided with a comprehensive training program and presentations about the fundamentals of FCC technology, as well as the most recent advances in FCC catalyst and additive technology. Some topics discussed included the chemistry of FCC, heat balance, unit monitoring and optimization, pressure balance, resid processing, and an extensive session on troubleshooting. The final session included an informal quiz to reinforce the learning experience, and was concluded with a certification ceremony. Orpic, which is owned by the government of the Sultanate of Oman and by Oman Oil Company SAOC, is one of Oman's largest companies and is one of the most rapidly growing businesses in the Middle East's oil industry. It has refineries at Sohar and Muscat, as well as aromatics and polypropylene production plants in Sohar. The RT team periodically provides technical programs such as this around the world to customers and others in the industry. 40 Issue No. 114 / 2014

43 Global leader in hydroprocessing catalysts offering the complete range of catalysts and services Advanced Refining Technologies 7500 Grace Drive Columbia, MD USA

44 GRACE, MIDAS, CATALAGRAM, D-Prism, GSR, G-CON, OLEFINSMAX, OLEFINSULTRA and SuRCA are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. ACHIEVE and DCR are trademarks of W.R. Grace & Co.-Conn. ART, and Advanced Refining Technologies are trademarks, registered in the United States and/or other countries by Advanced Refining Technologies, LLC. ApART and 545DX are trademarks of Advanced Refining Technologies, LLC. Chevron Lummus Global is a trademark of Chevron Intellectual Property, LLC. ACE is a trademark of Kayser Technology. This trademark list has been compiled using available published information as of the publication date of this brochure and may not accurately reflect current trademark ownership or status. GRACE CATALYSTS TECHNOLOGIES is a business segment of W. R. Grace & Co.-Conn., which now include all product lines formerly sold under the GRACE DAVISON brand. Copyright 2014 W.R. Grace & Co.-Conn. All rights reserved. The information presented herein is derived from our testing and experience. It is offered, free of charge, for your consideration,investigation and verification. Since operating conditions vary significantly, and since they are not under our control, we disclaim any and all warranties on the results which might be obtained from the use of our products. You should make no assumption that all safety or environmental protection measures are indicated or that other measures may not be required. catalysts@grace.com